Mafic and ultramafic orthogneisses from the western Grenville Province of Quebec adjacent to the Archean Superior Province (Canada) display geochemical characteristics that highlight processes that shaped the pre-Grenvillian Laurentian margin through late Archean to Mesoproterozoic time. Group I mafic and ultramafic granulites of the Parautochthonous Belt compositions overlap Archean Abitibi metavolcanic rocks (komatiites to Fe-rich andesites) supporting their autochthonous character. Limited variation of incompatible trace-element ratios with increasing differentiation suggests minimal sialic crust assimilation during petrogenesis and probable formation in an oceanic setting. Group II mafic tholeiites occur within both the Parautochthonous Belt and the Allochthonous Polycyclic Belt. Their compositions differ significantly from those of Archean rocks but overlap those of Proterozoic and modern continental tholeiites. Group III mafic calc-alkaline amphibolites, predominantly in the Allochthonous Polycyclic Belt, display chemical characteristics expected of magma derivation from subducted oceanic crust. In contrast to group I Archean meta-igneous rocks metamorphosed during the Kenoran orogeny, group III rocks do not record an early phase of large-ion lithophile element (LILE) metasomatism and granulite-facies metamorphism. As such, their emplacement is interpreted to postdate the Archean Kenoran metamorphism and to be Proterozoic in age. Group I rocks reflect an Archaean ensimatic greenstone belt environment; group II tholeiites reflect a Proterozoic continental rift environment; and group III rocks reflect a subduction-related source, possibly related to Andean-style, calc-alkaline magmatism.